Hydrocarbon conversion process



United States Patent 26,188 HYDROCARBON CONVERSION PROCESS Charles Newton Kimberlin, Jr., and Elroy Merle Gladrow, Baton Rouge. La., assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Original No. 2,971,903, dated Febald, 1961, Ser. No. 638,232, Feb. 5, 1957. Application for reissue Aug. 24, 1962, Ser. No. 219,349

21 Claims. (Cl. 208-120) Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

The present invention is concerned with a process for the preparation of improved catalysts. It more specifically relates to the preparation of improved catalysts suitable for use in cracking, reforming aromatization, isomerization, polymerization and alkylation processes. In accordance with the present invention, an improved crystulline silica and alumina comprising catalyst is employed in these hydrocarbon conversion processes.

It is known in the art to improve the quality of hydrocarbons, particularly petroleum hydrocarbons, by treating them with catalysts under various operating conditions to effect the above-enumerated conversions. For example, it is well known to treat petroleum oils boiling in the range abov about 400 F. with a silica-magnesia or a silica-alumina catalyst at temperatures in the range of about 600" to 1100 F. in order to crack the oils and secure petroleum oils fractions boiling in the motor fuel boiling range. Similarly, it is also known to alkylate isoparafiins or aromatic hydrocarbons with silica-alumina cracking catalysts. it is also known that synthetic porous solids, comprising silica and one or more metallic oxides, such as alumina, magnesia, zirconia, beryllia, boria, and others, have catalytic properties for the treatment of petroleum hydrocarbons.

Heretofore, these catalysts have been prepared by variousprocedures. One method, for instance, is to prepare a silica hydrogel and impregnate the latter with a solution of a salt of magnesium, aluminum, beryllium, zirconium, or other desired metal salt, and then followed by treatment of the hydrogel with ammonia in order to precipitate the magnesia and/or the oxide of the added metal within the gel structure. Another method involves mixing dried silica hydrogel with magnesia and the oxide of the third metal. Still another has been to mull magnesia with the silica hydrogel in water followed by drying and activation.

From the preceding it is apparent that the general procedure for preparing these conversion catalysts is to prepare the silica hydrogel or hydrosol, mixing the same with magnesia to secure the desired silica-magnesia composition, and adding, if desired, oxides of group II, III, IV, VI and VIII metals, including zinc, titanium, aluminum, zirconium, cadmium, chromium, vanadium, copper and iron. By whatever means prepared, the final catalyst was amorphous and, indeed, if any crystalline material were present in the final product, hydrocarbon conversion was seriously adversely affected and byproduct formation increased.

These catalysts, while both very active and selective in their action on the hydrocarbon feed, have some drawbacks. These secm to stem inherently from the amorphous nature of the catalyst that one strives to achieve. The amorphous gels comprise pores covering a wide range of sizes, from less than about 5 Angstrorns diameter to as much as 200 Angstroms diameter or more. In the very line pores, a feed molecule encounters diffusion difficulties, with the net result that the feed molecules do Re. 26,188 Reissued Apr. 11, 1967 not have free access over all the surface, and the product molecules may not evaporate from the pore before being convened further to a high boiling hydrogen-deficient coke deposit. The coke deposit may cover up some of the active catalytic agent and also require more frequent regeneration of the catalyst by burning the coke off with air. All of these devices shorten average catalyst life.

The conventional gel type catalysts mentioned above comprising silica, alumina, magnesia, and other oxides in combinations of two or more components are acidic in nature. In the case of silica-alumina catalysts, it is generally considered that the strong acid site is formed by the condensation of SiOH and AlOH groups. The dis persion of these acid sites throughout the amorphous gel structure determines the ultimate performance of the catalyst. The more uniformly the active sites are dispersed, the better the catalyst. There should not be isolated regions of silica or alumina in the particular case with silica-alumina catalysts. The mechanism by which hydrocarbons react over gel type catalysts in which the catalyst is behaving like an acid is through the formation of carbonium ions. Carbonium ion type reactions are those involved in cracking, alkylation, polymerization, and isomerization. But to those skilled in the art the credo with gel catalysts has been: the more amorphous the gel, the better the dispersion, and hence, the better the catalyst. However, a catalyst has been discovered that shows high activity and selectivity while comprising a highly ordered crystalline material characterized by having pores of nearly uniform dimensions in the range of about 6 to 15 Angstrorns. This catalyst comprises an alumino-silicate anionic cage structure in which the alumina and silica tetrahedra are intimately connected to each other. Hydrogen or various metal cations are distributed throughout the structure to maintain electrical neutrality. The dispersion of the silica and alumina tetrahedra is highly ordered, thereby making for a maximum number of active sites caused by the condensation of SiOH and AlOH groups. It is hard to conceive of how a structure could be built having more active sites, be it either amorphous or crystalline. The uniform pore openings in the range of about 6 to 15 Augstroms allow for easy ingress of all hydrocarbon feed types and egress of the reaction products. This serves to lower catalytic coke buildup within the structure and improve regeneration characteristics of the catalyst.

The catalyst of the invention, as mentioned above, is a crystalline alumina-silicate and can be base exchanged with numerous metal or hydrogen cations. In this regard it resembles a zeolite, some of which are known to possess activity as cracking catalysts. However, the catalyst of the invention may be distinguished over the zeolite art by the nearly uniform pore openings.

In accordance with the present invention, there is employed as a hydrocarbon conversion catalyst a metal salt of a crystalline alumino-silicate having pore openings adequate to admit freely the individual molecules to be converted. The pore openings will therefore be about 6 to 15 Angstroms. Random size openings are not satisfactory when they cover a wide range for the reasons mentioned above.

Alumina-silicates of high conversion activity may be prepared by mixing and heating sodium aluminate and sodium silicate, preferably sodium mctasilicate under carefully controlled conditions of temperature, concentrations, and alkalinity, to produce a crystalline product which is subsequently dehydrated under conditions to preserve the crystalline structure. The sodium content of the alumino-silicate is thereafter replaced at least in part by effecting ion exchange with the appropriate metal salt, such as magnesium.

The preparation of the catalyst involves the maintenance of several critical steps. These are (l) the ratio of soda to silica, (2) the reaction temperature, (3) the pH of the solution from which the sodium aluminusilicate is crystallized, and (4) the ratio of silica to alumina. Unless these critical conditions are observed, the resulting composition will either not be crystalline, or it will have little or no adsorptive properties, the pores will not be uniform, or the pores, if uniform, will be too small to admit any but small diameter molecules. If the conditions are observed, the pores will be large enough to admit most organic molecules, and will be between 6 and 15 Angstroms.

The ratio of Na O/SiO, in the silicate employed must be at least 0.5/1, but may be as high as 2/1. Preferably, the ratio is 0.7/1 to H1, and the desired reagent is sodium metasilicate. If water glass is employed, additional caustic must be present.

The composition of the sodium aluminate is less critical. Sodium aluminates having any ratio of soda to alumina in the range of 1/1 to 3/1 may be employed; however, a sodium aluminate having a high ratio of soda to alumina is preferred, and a sodium aluminate having the ratio of about 1.5/1 Na,O/Al,0; is particularly desirable. The amounts of sodium silicate solution and sodium aluminate solutions are such that the mot ratio of silica to alumina in the final mixture is at least 2.2/1, and preferably 2.5-4/1. However, silica to alumina ratios as high as 10/] may be employed.

The method of mixing the sodium metasilicate and sodium aluminate solutions must be carried out in a manner allowing formations of a precipitate having a uniform compo ition. A good method is to add the aluminate to the silicate at ambient temperatures using rapid and eflicient agitation to make a homogeneous paste. Thereafter, the mixture is heated to about 180 to 215 F. for a period up to 200 hours or more to ensure crystallization in the form having interstices large enough to adsorb isoparafiinic and aromatic molecules. The heat-soaking step is essential; however, heating at temperaturcs of about 350 F., and higher does not produce a crystalline composition having the desired uniform size pore openings.

A general scheme for preparing the hydrocarbon conversion catalyst is as follows: A solution of sodium metasilicate is prepared, having a concentration of 30 to 300 grams, preferably 100 to 200 grams/liter. Similarly, a solution of sodium aluminate having an A1 concentration of 40 to 400 grams, preferably 200 to 300 grams, is prepared. The amounts of metasilicate and aluminate solutions employed are such that the ratio of SiO /AI O in the final mixture is 2.2/1 to /1, preferably 2.5/1 to 4/1. The solutions are mixed, preferably at ambient temperatures. The slurry is of such concentration that the pH is above 12. Considering the amount of sodium atoms present in the total composite, the total volume of slurry should be adjusted so that each liter of composite slurry contains about 2 to 6 equivalents of sodium, preferably about 3 to S equivalents of sodium. The resulting slurry is heated from 180 to 250 F., but below 300 F., for a period of time depending on the temperature. At 210 F., this is about 3 to 24 hours, and shorter at higher temperatures, although long heating times may be employed without producing any deleterious effects.

The crystalline product resulting from the heat-treating step is then preferably reacted with the salt of a metal of the type previously enumerated to prepare the active catalyst, though for some catalytic purposes the sodium form itself may be employed. In the latter case, the crystalline material is water-washed, filtered, and heat activated by calcination at 400 to 1000 F., preferably about 700 to 900 F. The crystalline sodium aluminosilicate formed during the heat soaking period has the stoichiometric composition of Na,O.Al O,.2.7SiO;. In

the majority of cases, however, it is desirable to convert the sodium form of the alumino-silicatc crystal to a more active form. For this purpose, the sodium crystals are reacted with metal salt solutions that enhance the catalytic behavior. These metals are of the type already enumerated, and may further include cobalt, nickel, copper, calcium, magnesium, chromium, iron, silver, gold, platinum, zinc, cadmium, rare earths, mercury, lead and the like. For hydrocarbon conversion catalysts of the cracking or alkylation type, it is particularly desirable to exchange the sodium with magnesium; for aromatization, with chromium or zinc or platinum or palladium; for hydrolorming or hydrodesulfurizntion, with cobalt, iron, or platinum.

When reacting the crystalline sodium alumino-silicatc with another metal salt solution, it is only necessary to replace about two-thirds of the soda with the other metal oxide. The removal of more soda than this does not bear too great an influence on the behavior of the crystals as catalysts. In the specific case of the magnesium form of the alumino-silicate, the relative stoichiometric composition is about 0.33 Nt o. (0.67 )MgO.Al O .(2.7)SiO By modifying the conditions of synthesis, it is possible to obtain crystals having pores between about 3 and 5 Angstroms diameter. Other metal forms of this crystalline sodium alumino-silicate may be prepared in a manner identical with the above 6 to 15 A. pore diameter crystal. The reactions which the 3 to 5 A. pore di ameter catalyst will promote are identical with the same metal form of the 6 to 15 A. pore diameter material. However, the 3 to 5 A. pore diameter crystals will not allow any but straight chain paraifins and olefins to enter the interior of the pores which present the active catalyst sites, Thus, branched chains, acyclics and all ring hydrocarbons are excluded from the catalytic sites, thus restricting the versatility and usage of this material as a catalyst. For the same reason as was advanced for high carbon deposits in the minute pores with gel type catalysts, the 3 to 5 Angstrom pore diameter crystals also yield relatively large amounts of catalytic colte. This limits the use of the 3 to 5 Angstrom material as a catalytic agent.

The process of the present invention will be more readily understood by reference to the following examples illustrating the same. The catalytic reactions involved, such as cracking, alltylation, isomerization and the like are so well known that they need not be redescribed, in that the process for carrying out the reactions form no part of this invention, save the employment of the catalyst. Thus, catalytic cracking may be carried out in fixed bed or fluidized solids bed operation at temperatures of 800 to 1000 F., and pressures of 0 to 200 p.s.i.g. in a manner known per se. Catalytic alkylation, particularly of aromatics, is normally carried out in a fixed bed at temperatures of 400 to 850 F., and pressures of 0 to 1000 p.s.i.g.

EXAMPLE 1 A sodium alumino-silicate having pore openings of about 4 Angstroms was prepared as follows: Four liters of water are heated to near boiling. A separate vessel contained 6 kg. of a solution comprising 1176 grams sodium metasilicate (Na OSiO A third vessel contained 1970 cc. of a sodium aluminate solution comprising 20% A1 0 and 1.5 mols Na O per mol N 0,. The hot water was rapidly stirred and the silicate and aluminate solutions were added simultaneously through separate lines to the vessel initially containing the water. The temperature was kept at 210-215 F. for a total of S0 minutes. The slurry was filtered and washed well with water. A chemical analysis showed it to have the relative stoichiometric composition of Na rO.Al2 )3.2Sl (Jj;. This material was heat activated for 4 hours at 850 P.

It had pore openings large enough to admit ethane, but it displayed no absorptive capacity for tuheptane. It is designated as catalyst A in suceeding examples.

EXAMPLE 2 A porti n of catalyst A. prior to heat treatment, was slurricd with a solution of calcium chloride, filtered. water washed, and heated for four hours at 850 F. This crystalline material having a molecular composition of (0.28 )NQ OHL'H ;(a().Al O .l'2)SiO had an absorptive capacity for nhcpt.tne of 0.19 cc./gram. lts pore opening was 5 Angstrom units, and is desiganted as catalyst EXAMPLE 3 A 250 gram portion of catalyst A" was slurried in l200 cc. of MgCl;, solution for one hour. After filtration, water washing and re-slurrying were repeated three more times. The final filter cake was dried and heated for four hours at 850 F. Analyses of the composite showed that about 6L6 mol percent of the original soda content had been replaced with magnesia, and it had an absorptive capacity for n-heptane of 0.12 cc./gram. It corresponds to a composition 0.38Na ollblhlgo.Al o lsio has a pore opening of. Angstroms, and is designated catalyst EXAMPLE 4 A crystalline sodium alumino-silicate having a uniform pore opening of about 13 Angstroms was prepared as follows: forty-three hundred and fifty grams of sodium metasilicate iNilgO.SlO2.5 'IJ()) are dissolved in 13 liters H O at room temperature. Using rapid stirring. 2650 grams of a sodium aluminntc solution (20% M 0 and LSNa OAI O molar composition} are added to the silicate solution. An additional l0 liters H O are added to facilitate stirring. The composite slurry is heated to 180 to 210 P1. and maintained at these temperatures for 240 hours. The slurry is cooled. filtered. and washed well with water. After oven drying at 250 F. and calcining for 4 hours at 850 F.. the material was analyzed and showed the relative stoichiornetric composition of Na QAl OJZISEO The product had an adsorptive capacity for n-hcptanc and toluene of about 0.20 ccngram. This is catalyst DY EXAMPLE 5 Five hundred grams cl pelleted catalyst "D" were slurri-zd in a liter of \-.zil'. and 1500 cc. of 12% MgCl solution as :tddcd. The composite "was stirred for two hours, the liquid decanted, and the pellets washed twice with 500 cc. Water. The ba e exchange operation was repeated two more times with fresh 12% MgCl: solution. The wet pellets we re dried in an oven at 250 F. and calcined 4 hours at 850 F. On analysi 76% of the soda had been replaced by magnesia. The resulting product. catalyst had an adsorption capacity of 0.l3 cc. n-heptancvgram and had a uniform pore size of about 13 Angstroms diameter.

EXAMPLE 6 A typical synthetic zeolitc DouciP comprises a plural gel, containing three components. viz. Ni|3(), A1 0 and 510 To determine the cracking properties of this zeolite. a ponion of this sodium aluminum silicate was dried, ground. pilled, and activated at 850 F. This product is catalyst "F."

EXAMPLE 7 This example illustrates the preparation of a magnesium form of a synthetic zeolite "Doucil." Commercial Doucil. the trade name for a good grade of sodium aluminum silicate, was ground and contacted with a mag nesium chloride solution until all the readily replaceable Na O was removed by base exchange to form largely magnesium aluminum silicate. This product. after washing until it gave a negative test for chloride ion, was dried. ground, pelleted. and activated by heating at 850 F. This material is referred to as catalyst G."

EXAMPLE 8 These catalysts were used to crack an Fast Texas light gas oil. The catalysts were made into -"-5,;" flat cyiindrit-al pellets and tested for cracking activity in a lixctl lit-d testing unit at 850 F., and 0.6 vol. of teed vol. of catalyst/hour for a two hour cycle. The results obtained are tabulated as follows:

The standardized test has been described by Conn and Connolly in Ind. Eng. Chem. 39. H38 tl 47I. and is set forth in US. 2.636.845. The sum ol D -l or distillate plus loss. is a criterion of nctiiity and selectivity, shoning the yield of desirable product. The XLidlln? gas production factor. GPF. and the relative carbon producing factor, CPF. are indicative of the amount of gas and carbon formed in commercial fluid cracking plants.

These data show that by far the highest catalytic zictivity was shown by the magnesium alumino-silicatc catalyst F." having a pore opening of about 13 Angstrom unit The same catalyst also showed the highe t selectivity to desired gasoline product, i.e. loviest GPP and GF.

EXAMPLE 9 Catalyst "E" above was regenerated by burning oil the coke at 850' F. and retested. In the second cycle it showed 45.0 vol. percent D-t L. a OPP ot 0.9 and n CPF of 1.37. it is thus seen that the catalyst is readily regenerable to full activity and selectivity.

EXAMPLE l0 Catalysts "D" and "E" were tested for .tls lutinu activity by contacting with propylene and toluene mixtures at 850" 1 and atmospheric pressure l'ced rates new about 0.64 v.. liour for the toluene and about 5 mols These data show that while the sodium form f the alumino-silicatc has some nlhylating .icli ity. the ll|l !ll\.'\i um form is considerably more acti\ c. That these alkaline reacting catalysts hate any alkylation activity at all is surprising. Normally. powerful clcctrr hillc reagents, such as the Friedel-Crafts type catalysts. the aluminum, iron, tin, zinc. etc. halides. H 50 lll", P 0 etc. are employed. Indeed, with ll'lCl-ll halides. HCl or lillr is essential for catalysts. The recognized .ilkylation catalysts are acidic in nature; the sodium form of the aluminosilicate, however, in an aqueous suspension shows a pH of about 10-11.

Furthermore catalysts C and E contain suhstuntial amounts of residual soda, namely 12.7 and 9.2% Na O respectively. Inasmuch as conventional gel type catalysls are acidic in nature and are poisoned by soda content above about 0592 M1 0, the high cracking activity Ullnintfd ith thew: catalyst is particularly surpri ing lwl lzncfipecl d.

Wiint is claimed is:

[L A nrucew for upgrading hydrocarbons vihich comprimes contacting ll hydrocnrbonaceous fiuid in a con \cninu zone ill clcvuted temperatures with a crystalline nietnllic :llumindsilicule catalyst halving uniform pore upcning l-ctuccn about 6 and ahout l5 Angstrom units, mid nititcrit'd cing the sole cnnversion catalyst in said mnc .ind rccmering 51! upgraded hydrocarbon product hiring a molecular eight no higher than mid first named h drocrbonnccou fluid] [2. The prom of claim 1 herein said catalyst comprm-s .i rncrnhcr oi the nkziline earth group] [3. in; prim of cluim 1 wlicrcin suid catalyst cumpry '1 mm. er t the plntinum group] [4 The rrncew of clnitn 1 uhcrein said catalyst com- ;ri-e- Ll member of the iron group] [5. The f l) C of cl.;im 1 herein said catabst compriws chromium] [6. The rucew of claim 1 wherein aid catalyst has the empirical formula here ME. is metal and n the valence thereof] [7. The procc of claim 1 herein a gas oil is cracked in :he prcwnce of said catalyst and the metallic aluminosilicate comprises mngnmium] [8. Tue pruce n1 claim 1 wherein a hydrocarbon stream i3 isumerizcd in the prcsence of said crystalline meml ic liillltliltDwillullC cnt;ily t.]

[9. The [h'l' ciw ul claim 1 wherein a hydrocarbon tzcum i- .trumtuizcd in the presence of said crystalline metallic rilumino-siliccuccatalyst, said alumino-silicate being ul -1nntinlly free of exchnngeable sodium and selcctcil from the claw comisting of chromium, zinc, platini-ni 1ml mllndium nltuuino-silicates.]

U0. The procew of claim 1 wherein a hydrocarbon -tru in. i, hytzwfnrmc-J in the prcwncc of said crystalline rictnl h ..lumino-si icuie cumlpt, said alumino-silicatc being ul nlnttillv free of exchangeable sodium and selected t'rurn t n: clzm cuneisting of cobalt, iron and platinum alurninol 'xnmj [11. A prose for cracking a gas oil which comprises wntcnling mid feed at a temperature of about 800 to W F. and Ill a prewsurc of about U to 1000 p.s.i.g. with .t can! -t cnn kting ssentially of a crystalline magnesium fil liilln .l-' lluill'l tuning a uniform pore opening of about (i to l? A gnrom units] [3. A pmccw f r upururlinc hydrocarbons which (0mrrnt's r nz uling a huh-0mrbunacenus fluid in n com-ern J n u! c mm'cd le'mpcrnlurcs with a crystalline rtrullic uluuu'nmilicatc curulys! having uniform pure L'lllllllpfi l'r'lu'eru about 6 and about 15 Angstrom units, .nift/ uuntrinl luiuc the SUlU cuni'emion catalyst in said :wni' and wintering an upgraded hydrocarbon product l. i am u run/m lrlrir wright no higher than said first ncum'd h i'lr-u (ll'll' nuc. nus fluid.

13. Thu prm'mr uf (laim 12 wherein said cauilyrt u rm' iwi a meui u'r u] the alkaline earl/i group.

14. A h il 'u' (Jil H1 (Ulll'LHlfl/I pmcess which unfr zm' (nun-1. Ill? 1: hulrucnrl on fluid in a conversion zone Hutton rwgmmuum, urnlt'r conditions in ether 11 ("fl!1'r uli i i .sml hytlmiurlv/n fluid, with a crystalline l ltiril r (.l'i'llilllll -lll"!l.' cumin! having uniform pore wi l uurzw lur win u w lit 6 and ulmul l ANQHI'UIH unirr. tilll u ruri'ul lnuzv rlu' .mlc (rmrenion catalyst in suit! m' will rr'imirim: u (cure/furl llydrucnrlmn [7f('(ll((l l r ls: n iclr! r10 luc'lur than said first nnuiul lrhhm nrlwn lluiil.

15. 'l'lu urn] u claim l1, wherein said cam/yr! cum- [l-l u lluuilu'r u] rlu' alkaline earth group.

'.= y w w ll 16. The proccxs of rluiui l4, \t'll(i'('lll min mlnlylf iompriiar a member of the plat num pinup.

17. A process for cracking a gut oil which munprisruv cnnmcliur: .iuid fr'ca' at (I u'mpvmlurv (rl ulwul 800 n; 1000 F. and (:1 a pressure of uhnul 0 (0 H p..r.i.g. with a cutulyr! consimliuq crxc'nliully of u cryalulliuc nmgntxsiunz (liIUHlllr)Slll((iI( [luring a uniform pore Opening 0 alum! 6 to 13 Anuslrum units.

18. A hyilmcarluui (mu-ennui procms which cornpr-ises conmcliug' a hydlucurhnn fluirl in n mmrmion t ne in (Ill clrl'nl'ctl rrmfwmlure wiilz a crystalline murallu' aluminumliiuu' t'il.'|ll \'\l inn-lug uniform pure inn uingx luiuccn rilmu! 6 and ulwun l5 lngurnnz unlit, Alli! cuml \'.\t having bfFll prvpiu'ml hr hnir' zzuluuun' 0/ the Mill uni form of lhe ('I). l4llllll' u/uuu'uu-liluuu with n mum: in .i'uhilunriully rmlucr i/s smliuui (unicnr uuui ihm HI!- pl'mc in i'nlulylic aln'lliy fur cur/Mug out will r'nutvrsinu, nrul rival-firing a cunrr'rrml hytimcurliun pimluc! Inning a molecular weight no higher than soul flIAl-litllllt'll ll \'|:l!U ('(II'lJOIl fluid.

If). llzv [)HM'LUX (ll tlt'u'ui l8. \rlu'ruin u lrwlrocurlmn .su'r'am is isumcrizcd in {he prmvncc 0/ mill i'ryxmllinc mcrallic aluminouihcuic cruulyil.

21 The proccrs' of claim 18, nhert'iu n l wlmcarhnu stream is urmnau'zcd in 1/10 prc'scm'c of will cryA'lu/line mr mllic almuinu-silic(no (illlll} l, sru'zl alumina-.u'licalc living .wlbsmnliully ire! of ur-hungml-lc .uulium and AC- lzcu'rl from t/uclaw unwilling of r/u'urnuuu, zinc, Ila/inuui L'lllll palladium u uuiiliiw'illcuu's'.

22. The prom-5s vl rluiul 18, wlu'reiu a hydrocarbon .vucu/n ix lrwlruftu'mt'il in rlu' fl't'ACllLt' u) .suiil myxtrllliuu nmuillic aIruni/imn imlc cumlyw, .Sdlll ulmuinn-rilirrne brine substantially ji'm nj rxclumucuhie sodium and selccu'd from the clam consisting of cohull. iron and pluti' num alumino-silimies.

23. The pruccss 0f cluim 18, wherein higher molecular wcight hydrrn'urhoux are crucial into lower umlvc'ulur wright hydrocarbons.

24. A hydrocarbon runw'rsivn process which (runprisrs cunlacriny a hyilmrurlun fluid in n l'fll'llfl' 'lllli zone or an elevated rvmpcruum' Will] u crystalline ulumimr-xilicute analyst having unihuur nm' upmiugr hrrwvcn about 6 and about 15 A., mid ulunriuu-xilimec hut-in the major portion of its cation crunch! .supplir'cl by a ration other than sodium, and laurel-lug a coui'vrrul hydrocarbon product having a molvc'ular ucig'ht n0 higlu'r than said first-named h \'(l'rucnrl10n fluiil.

25. The PI'OC('.\S of claim 24, n'lzvrcin will rruion other than sodium comprin's an ullt'ulim' mrlh uutru'.

26. Tim procem of claim 25, Hll(l(.ll1 hiya/irimnlt'culur weight hydrocarbons are cmcktn' inlu lmnr molecular weight hydmc'arhnnr uml .Vllll ulltulinv mirth nu'ml ix magnesium.

27. The process of claim 24, whrrcin mill union uther than sodium c'rmzprixvs a rare earth mclul.

28. The prmew 0] cla m 2-1. whr'rt'in mid r'utiou other than sodium cnmprircr a plulinuui gnu/p nulul.

29. The prmzgsr of (loin: 25, whirl-in mu! alkaline" earth meml is i'nlriuru.

30. The pmccsi of (hu'ui 34, wlu-rr'ln higher mulvculnr uciglil lljill'l/Filll lillA mu rrmlmil lulu lmrur nmlci'ulur wright hytlroi'nrlmus null ilw pun (mini/ms (If mid rumlyll have a dlalm'li'r u/ u mul l} A.

31. A hjrilmc'arlmn rwuirrliun [u'iu't'rv which (01m prism corilucl'ing a llj'l/ll/(Yll'bflll fluid in :1 conversion :muat an c elmwl ltlllit'ltllllll will: (i rrvruillinc aluminn-silicate cuiulyi/ luu hug zuu'lru-m ,wu'u ope-'1 inns lu'ni'vi'n alum! 6 mm (slum! 15 ,-l,, said n/u minrmilu'mc living lulunus/lull jrtw 0/ rau'lzuuycuble .voilium, and rcrorr-riuu a uuzri'ru'd hyrlrin urlmn pmrluct hating a molecular weigh! in) highcr lluzn said firstmmu'il ltynmcurl n flu-ll.

10 32. A process for cracking a gas oil which comprises UNITED STATES PATENTS contacting said gas oil at a temperature of about 800 to 1000 F. and at a pressure of about 0 to 1000 p.s.i.g. 32322553 1222 with a crystalline metallic alumina-silicate catalyst hav- 2834429 5/1958 Kinsella 3 ing uniform pore openings between about 6 and about 5 2904607 9/1959 Mano, 15 A., said alumina-silicate having the major portion of 2962435 11/1960 Fleck at a 9 its cation content supplied by a cation other than sodium. 297l'904 2/1961 Gladmw 208*135 References Cited by the Examiner Th f u f d b h E f DELBERT E. GANTZ, Primary Examiner.

e o owing re erences, cite y t e xaminer, are 0 10 record in the patented file of this patent. or the original ALPHONSO SULLIVAN Examme" Patent. S. P. JONES, Assistant Examiner. 

